LIQUID MEMBRANE SEPARATION PROCESS

A SHORT REPORT PRESENTED TO CHEMICAL ENGINEERING DEPARTMENT UNIVERSITY OF MAIDUGURI MAIDUGURI, BY

ISIAK ISHOLA ATANDA 08/05/02/043

IN PARTIAL FULFILMENT OF THE COURSE CHE 405 SEPARATION PROCESS (II) DECEMBER 2012

1.0: Introduction to Liquid Membranes What is a Liquid Membrane?

A Liquid Membrane is just what it sounds like. A membrane made of liquid. It really isn't that outlandish of an idea; it's a simple membrane principle, just with a non-rigid material. And because of the nature of a liquid, liquid membranes circumvent problems other, more conventional membranes encounter, but they run into a whole different class of problems. One of the benefits of using a liquid membrane is that LMs are highly selective, and, with the use of carriers for the transport mechanism, specific molecular recognition can be achieved. LMs are relatively high in efficiency, and as such, are being looked into for industrial applications. There are, in fact, two basic types of liquid membranes, an Emulsion Liquid Membrane (ELM), and an Immobilized Liquid Membrane (ILM), also called a Supported Liquid Membrane. An ELM can be thought of as a bubble inside a bubble inside a bubble, and so on; the inner most bubble being the one recieving phase, all the others acting as separation skins with carriers inside, and anything outside the bubble being the source phase. In an ELM setup, there would be huge quantities of these bubbles, of course, all doing the same thing. An ILM is much simpler to visualize. Pretty much what you have is some other kind of rigid membrane, with lots of microscopic pores in it. Every one of these pores, then, is filled with this liquid, and in that liquid, you have the organic liquid and the carrier liquid. What happens then is that the ILM takes things from one side of the rigid membrane and carries it to the other side through this liquid phase. And that, my friends, is pretty a very brief model of what a LM is. Liquid Membrane Types Basic Overview of Membrane Design

While there are two generic types of membranes, five different setups have been studied in an effort to increase the efficiency of the entire liquid membrane operation.
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Bulk Liquid Membranes Emulsion Liquid Membranes Thin Sheet Supported Liquid Membranes Hollow Fiber Supported Liquid Membranes Two Hollow Fiber Supported Liquid Membranes

Bulk Liquid Membranes: This setup is useful only for laboratory

experiments, and is set up as follows. Following Figure 1, a U-tube cell is used, and some type of carrier, perhaps dissolved in CH2Cl2, is placed in the bottom of the tube. That is the organic membrane phase..

Figure 1. Bulk Liquid Membrane.

Emulsion Liquid Membranes:This setup has a very thin membrane and a

large surface area per unit sourcephase volume, which enhances the transport rate of this membrane.

Figure 2. Emulsion Liquid Membrane.

Thin Sheet Supported Liquid Membranes:The most simplistic in

design, the thin sheet supported liquid membrane can be utilized for laboratory scale, but cannot be scaled up for industrial use. Essentially, this is just pushing the fluid out.

Figure 3. Thin Sheet Supported Liquid Membrane.

Hollow Fiber Supported Liquid Membranes:The design of the HFSLM is

akin to a large electrical cable. You have the outer shell, which is a single nonporous material, through which the materials inside cannot be transported.

Figure 4. Hollow Fiber Supported Liquid Membrane

Liquid Membrane Transport Phenomenon

Types of Transport
The four types are ;
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Cation Transport Anion Transport Neutral Guest Transport Switchable Transport

Cation Transport
Cation Transport can occur in either of two ways, either symport or antiport, as shown in Figures 8 and 9. In the symport configuration, a neutral carrier moves the guest and cotransported anion together across the membrane. This occurs in four stages. If the outer side of the membrane is in contact with Aqueous Phase I, and the inner side of the membrane is in contact with Aqueous Phase II, then 1. At the Phase I interface of the membrane, the guest salt is complexed with the carrier. 2. That complex diffuses across the membrane. 3. The release of that guest salt occurs at the Phase II interface of the membrane.

4. The carrier diffuses back across the membrane, ready to continue.

For the antiport transport, though, you utilize an anionic carrier, so the four stages are a slight bit different.
1. At the Phase I interphase, the carrier tries to form a neutral complex with the guest cation. 2. The ion-pair diffuses across the membrane. 3. Cation-exchange reaction releases the guest cation to Phase II. 4. The carrier complex with the counter-transported ion diffuses back across the membrane.

Since the mechanism of transport in symport is effectively M+ and X- being transported simultaneously, the symport transport has a concentration gradient of

Now, the concentration gradient for the antiport is slightly different; the mechanism is distinctly pH-dependant. This relationship shows itself in the extraction constant, and this effects the concentration gradient equation, which is now

Anion Transport
As you can see in Figure 10, anionic transport is similar in mechanism to the cationic transport, save for the use of a cationic carrier instead of an anionic one in the antiport configuration. Neutral Guest Transport Neutral species are transported symport, using various carriers. Oxygen and CO have been transported as gases through the liquid membrane, but they use a mechanism different that that shown in Figure 11, or so researchers theorize.
Switchable Transport

The use of photo- and electrochemistry has recently been investigated into increasing the rates at which the carrier complexes dissociate, which would, therefore, increase the transport rate. A sample of this is shown in Figure 12, but you can use your imagination to come up with exactly what is being down. Essentially, the switchable transport system works in addition to the regular transport system, and only the second step of the AC - e--> AC+ --> A + C- reaction is accelerated.

2.0:

Governing Principles

There are several ways in which we can set up a liquid membrane system that will accomplish what we need it to do. There are in fact two major categories of liquid membrane transport, active and passive transport,and these two stages involve diffusion, therefore the rules governing diffusion is an important Governing Principle in LMS;

Rules Governing Diffusion

Simple Diffusion
The flux of a gas through a membrane under a concentration gradient along the x axis is dictated by Fick's First Law;

If one happens to apply a potential across a system, things become a little shaky if you continue using Fick's Law. Therefore, we resort to the Nerst-Planck equation,

If there is no electrochemical potential, we can use the Einstein equation to predict the diffusivity.

Constant Concentration Gradient

If you assume there is a constant concentration gradient, dC/dx over the entire diffusing region, you can integrate the dC/dx term as a function of the distance, x. In doing so, you realize that at steady state, the flux is constant over the diffusing distance, independant of x. The Nerst-Planck Equation, as shown before, is suddenly rewritten as

And as the electrochemical potential goes to zero, Fick's First Law becomes

Antiport Mechanics
In the antiport typical model, the dissociation constants for the complexes are defined by the equation

where i and j are components in the phases, and X refers to the carrier. If there is no j in phase I, then the equations for flux of species i from phase I to II and from II to I, as well as the overall flux are

The above equations are not really helpful for most people, so I'll explain a little. The really interesting thing is the point at which the overall flux becomes zero, which is when

Thus, you now have a range over which the uphill transport and downhill transport is possible. If the left hand side of the above equation is greater than the right hand side, then you have uphill transport. If the left hand side is less than the right, you have downhill transport, so long as the left is above zero.

A Few Words on Fick's Law

Essentially, Fick's Law breaks down like this.

Ji is the flux Di is the diffusivity dC/dx refers to the concentration gradient in the direction of travel across the membrane.

This law work for systems with neutral species and any system with charged species but no applieCOVEd potential.

A Few Words on the Nerst - Planck Equation

The NerstR-Planck equation refers to several new variables.

u is the mobility of an ion. F is the Faraday constant. The phi refers to the electric potential across the membrane. z is teh valency of the ion. X refers to the force associated with the electrochemical potential and is defined by the equations

3.0: INDUSTRIAL APPLICATIONS ROOFING SYSTEMS

Liquid Membrane System is ideal on concrete decks in both new construction and re-roof applications. This proven technology is perfect for roofs with numerous penetrations since it easily conforms to any shape and provides a seamless, membrane that will stand

the test of time. It is also ideal for use as waterproofing for plaza decks or as a stand alone roof membrane.

ZINC RECOVERY FROM WASTEWATER IN TEXTILE INDUSTRY

Precipitation of Zn(OH)2,ZnS or ZnCO3 from wastewater is carried out in Textile industry by Emulsion Liquid Membrane method. RECOVERY OF URANIUM AND COPPER In this method 90% of Uranium is recovered and is concentrated to 6g/dm3 in Nuclear industry. BUILDING INSULATION When faced with a confined urban space, numerous roof penetrations or restricted use of hot asphalt or heat welding, liquid-applied systems provide a seamless waterproof membrane that is easily applied and conforms to any penetration shape.

ADVANTAGES AND DISADVANTAGES OF LMS OVER OTHER PROCESSES LMS is advantageous over other separation processes for the reasons outlined below: Very high separation selectivity. Mass transfer can take place on carriers. No expensive pre-treatment is necessary. Solutions of product can be concentrated Process costs are relatively low. LMS is also disadvantageous as unsolved problems cover the coalescence of emulsions and dissolution of membranes and substances they contain in the phase.

4.0:

5.0: REFERENCES WODZKI R., Polimery,41,426,1996. SCHLOSSER S, Advances in membrane phenomena and process ESMST Summer School pp 178 1988. SCHLOSSER S, KOSSACZKY E,J Radioanal nucl. Chem.,101,pp 115-125 1986. LIN.N., AIChEJ, 17,459,1981.

NERNST W. RIESINFELDE. H. Ann. Physic, 8, 1902.

Pinnau, I., Freeman, B.D., Membrane Formation and Modification, ACS, 1999. Osada, Y., Nakagawa, T., Membrane Science and Technology, New York: Marcel Dekker, Inc,1992. Perry, R.H., Green D.H., Perrys Chemical Engineers Handbook,7th edition, McGraw-Hill, 1997.